吡啶硫酸氢盐离子液体催化甘油与乙酸酯化反应动力学

doi:10.11949/0438-1157.20200186

摘要/Abstract

摘要：

以吡啶硫酸氢盐离子液体为催化剂，系统研究其催化甘油和乙酸酯化反应生成三乙酸甘油酯的动力学行为。采用单因素实验考察反应温度、酸醇摩尔比、催化剂用量等因素对甘油转化率及产物三乙酸甘油酯收率的影响。根据拟均相一级反应机理建立微分方程组模型，通过动力学数据拟合获得指前因子和反应活化能。结果表明：甘油转化率随反应温度、酸醇摩尔比升高而增加；随着催化剂用量的增加，甘油的反应速率逐渐增大，但平衡转化率基本不变。当反应温度为110℃，乙酸/甘油摩尔比为6∶1，催化剂用量为甘油的3%（质量分数）时，甘油转化率最高为98.5%，三乙酸甘油酯收率最高为40.4%。甘油与乙酸反应逐步生成单乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯的指前因子k₁₀、k₂₀、k₃₀分别为7.17、14.19、13.78 min^-1，其相应的反应活化能E₁、E₂、E₃分别为19.10、21.58、23.25 kJ·mol^-1，该动力学模型计算值与实验值吻合较好。该催化剂相较于已报道的Amberlyst-15、杂多酸催化剂反应条件更温和、选择性更高、反应活化能更小，具有更好的催化效果。

关键词: 离子液体催化剂, 吡啶硫酸氢盐, 动力学模型, 酯化反应, 三乙酸甘油酯

Abstract:

Using pyridine bisulfate ionic liquid as a catalyst, the kinetic behavior of glycerol and acetate into triacetin was systematically studied. The effects of reaction temperature, molar ratio of acid to alcohol, and amount of catalyst on glycerol conversion and triacetin yield were investigated using single factor experiments. The reaction kinetic model was developed using the quasi-homogeneous first-order reaction theory. The pre-exponential factor and the reaction activation energy were obtained by fitting the kinetic experimental data. The results showed that the conversion of glycerol increased with increasing of reaction temperature and the molar ratio of acetic acid to glycerol. With the increase of the amount of catalyst, the reaction rate of glycerol increased gradually, but the equilibrium conversion remained essentially unchanged. Under the optimum reaction conditions of temperature at 110℃, the molar ratio of acetic acid to glycerol in 6∶1 and the catalyst dosage of 3%, the maximum conversion of glycerol and the maximum yield of glycerol triacetate were 98.5% and 40.4% respectively. The pre-exponential factors k₁₀, k₂₀ and k₃₀ of glycerol with acetic acid gradually forming monoacetin, diacetin and triacetin were 7.17, 14.19 and 13.78 min^-1 respectively. The corresponding reaction activation energies E₁, E₂ and E₃ were 19.10, 21.58 and 23.25 kJ·mol^-1 respectively. The calculated values by the kinetic model were agreed well with the experimental values. The catalyst has a better catalytic effect than that of the reported Amberlyst-15 and heteropoly acid catalyst with milder reaction conditions, higher selectivity, and lower activation energy.

Key words: ionic liquid catalyst, pyridine bisulfate, kinetic model, esterification, triacetin

中图分类号:

TQ 032.4

徐浩,李洋,夏成康,何瑞宁,邹昀,童张法. 吡啶硫酸氢盐离子液体催化甘油与乙酸酯化反应动力学[J]. 化工学报, 2020, 71(11): 5178-5187.

Hao XU,Yang LI,Chengkang XIA,Ruining HE,Yun ZOU,Zhangfa TONG. Kinetics of esterification of glycerol with acetic acid catalyzed by pyridine bisulfate ionic liquid[J]. CIESC Journal, 2020, 71(11): 5178-5187.

图/表 10

图1 酯化反应实验装置图1—恒温油浴锅；2—温度计；3—三口烧瓶；4—取样器；5—冷凝管

Fig.1 Apparatus of the esterification reaction experiments

图2 不同反应温度下甘油-乙酸酯化反应体系各组分随时间变化情况

Fig.2 Variation of each component of G-AA reaction system with time under different reaction temperature

图3 不同酸醇摩尔比下甘油-乙酸酯化反应体系各组分随时间变化情况

Fig.3 Variation of each component of G-AA reaction system with time under different acid-alcohol molar ratio

图4 不同催化剂用量下甘油-乙酸酯化反应体系各组分随时间变化情况

Fig.4 Variation of each component of G-AA reaction system with time under different catalyst dosage

图5 最佳反应条件下甘油酯化产物收率

Fig.5 Product yield of G-AA esterification at optimal reaction conditions

表1 不同反应温度下的反应速率常数

Table 1 Reaction rate constants at different temperatures

温度/℃	k₁	k₂	k₃
65	7.9×10^-3	6.7×10^-3	3.5×10^-3
80	11.1×10^-3	8.9×10^-3	5.1×10^-3
95	13.8×10^-3	12.1×10^-3	6.9×10^-3
110	17.8×10^-3	16.5×10^-3	9.3×10^-3

图6 反应速率常数与反应温度的关系

Fig.6 Relationship between reaction rate constant and temperature

表2 甘油与乙酸酯化反应的指前因子和活化能

Table 2 Pre-exponential factor and activation energy of G-AA esterification

k_i	k_i₀/min^-1	E_a,_i/(kJ·mol^-1)
k₁	7.17	19.10
k₂	14.19	21.58
k₃	13.78	23.25

图7 不同反应温度下各组分变化的实验点与计算曲线的比较

Fig.7 Comparison between experimental points and calculated curves of changes in components at different reaction temperatures

表3 不同催化剂性能的比较

Table 3 Performances comparison of different catalysts for G-AA esterification

催化剂种类	最佳反应条件	甘油转化率	产物收率	反应活化能
Amberlyst-15^[38]	t=110℃, MR=9∶1, c_cat=82.86 mmol H⁺/L	α_G=97.1%	Y_MAG=7.6%	E₁=57.26 kJ·mol^-1
			Y_DAG=46.3%	E₂=31.87 kJ·mol^-1
			Y_TAG=43.2%	E₃=13.90 kJ·mol^-1
hetropoly acid^[39]	t=110℃, MR=9∶1, c_cat=8.51 mmol H⁺/L	α_G=98.2%	Y_MAG=23.4%	E₁=24.99 kJ·mol^-1
			Y_DAG=59.6%	E₂=28.10 kJ·mol^-1
			Y_TAG=15.2%	E₃=51.73 kJ·mol^-1
pyridine bisulfate ionic liquid (本文)	t=110℃, MR=6∶1, c_cat=129.04 mmol H⁺/L	α_G=98.5%	Y_MAG=11.5%	E₁=19.10 kJ·mol^-1
			Y_DAG=46.6%	E₂=21.58 kJ·mol^-1
			Y_TAG=40.4%	E₃=23.25 kJ·mol^-1

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